Tetracyanoanthraquinodimethane polymers and use thereof

ABSTRACT

Novel tetracyanoanthraquinodimethane polymers and use thereof. The problem addressed was that of providing novel polymers which are preparable with a low level of complexity, with the possibility of controlled influence on the physicochemical properties thereof within wide limits in the course of synthesis, and which are usable as active media in electrical charge storage elements for high storage capacity, long lifetime and stable charging/discharging plateaus. Tetracyanoanthraquinodimethane polymers consisting of an oligomeric or polymeric compound of the general formula I have been found.

BACKGROUND OF THE INVENTION Field of the Invention

The invention relates to novel tetracyanoanthraquinodimethane polymersand to the use thereof as active materials in electrical charge storagemeans such as secondary batteries. In secondary batteries of this kind,the inventive polymers can be used, for example, as active electrodematerial. These secondary batteries are notable especially for high cellvoltages, high power densities and long lifetimes, and also simple andscalable processing and production methods.

The 11,11,12,12-tetracyanoanthraquinodimethane (TCAQ) structures ofthese novel polymers exhibit exceptional electrochemical behaviour. Thisfeatures a reversible two-electron redox process, as a result of whichthe electrical charge storage means have a one-stagecharging/discharging plateau among other features.

Discussion of the Background

11,11,12-Tetracyanoanthraquinodimethane polymers are already known asactive components in organic electronic components. Thus, copolymers of11,11,12,12-tetracyanoanthraquinodimethane derivatives withcyclopentadithiophene units in the polymer backbone, synthesized via theStille reaction, are used as active material in solar cells (CN103159919 A).

Likewise known is the use of copolymers of11,11,12,12-tetracyanoanthraquinodimethane derivatives with triarylamineunits in the polymer backbone, synthesized via Heck reaction, as activematerial in solar cells, electroluminescent components and field-effecttransistors (CN 102796245 A).

Copolymers of 11,11,12,12-tetracyanoanthraquinodimethane derivativeswith metallocene units in the polymer backbone, synthesized viaaza-Wittig reaction, are used as polymeric magnets (US 2012/0035330 A1,CA 26995856 A1).

Known polymers having 11,11,12,12-tetracyanoanthraquinodimethane unitsare exclusively polymers in which the11,11,12,12-tetracyanoanthraquinodimethane unit is localized in thepolymer backbone. A typical structure of these polymers is representedby the following schematic representation:

In this representation, Ar is a bivalent aromatic group and n is aninteger which states the number of repeat units and hence determines thelength of the polymer.

The aforementioned 11,11,12,12-tetracyanoanthraquinodimethane polymersare difficult to prepare. The synthesis of these polymers requires twomonomers or the synthesis of a bifunctional monomer. The preparation ofsuch monomers comprises a multistage synthesis. In general, thepolymerization is conducted by palladium-catalysed cross-couplings(Stille reaction, Heck reaction, Suzuki reaction), which is the reasonwhy the monomer units have to have suitable structures such as boronicacids or esters thereof, double bonds or organic tin compounds.

The copolymer obtained is often no longer soluble and can therefore beprocessed only with difficulties. Moreover, there is a high degree ofmolar mass distribution in the case of these polymerization methods, andthe molar mass and yield are usually low. In addition, only conjugatedcopolymers are preparable for the most part in these known processes.

In the case of use in electrical charge storage means, these polymers,as a result of the high molar mass of their repeat units, would have alow mass-to-charge ratio and therefore too low a theoretical capacityfor practical applications. The through-conjugation in the polymerbackbone causes a change in the redox potential, which would mean thatthe electrical charge storage means would not have a stablecharging/discharging plateau either.

Therefore, there have been no reports in the specialist field about useof these 11,11,12,12-tetracyanoanthraquinodimethane polymers forelectrical charge storage means.

Organic radical batteries are electrochemical cells which use an organiccharge storage material as active electrode material for storingelectrical charge. These secondary batteries are notable for theirexceptional properties, such as fast chargeability, long lifetime, lowweight and high flexibility, and also ease of processability.

Some polymeric structures having a redox-active units other than theaforementioned 11,11,12,12-tetracyanoanthraquinodimethane polymers, incontrast, have already become known as active electrode materials forcharge storage (for example, WO 2012/133202 A1, WO 2012/133204 A1, WO2012/120929 A1, WO 2012/153866 A1, WO 2012/153865 A1, JP 2012-221574 A,JP 2012-221575 A, JP 2012-219109 A, JP 2012-079639 A, WO 2012/029556 A1,WO 2012/153865 A1, JP 2011-252106 A, JP 2011-074317 A, JP 2011-165433 A,WO 2011/034117 A1, WO 2010/140512 A1, WO 2010/104002 A1, JP 2010-238403A, JP 2010-163551 A, JP 2010-114042 A, WO 2010/002002 A1, WO 2009/038125A1, JP 2009-298873 A, WO 2004/077593 A1, WO 2009/145225 A1, JP2009-238612 A, JP 2009-230951 A, JP 2009-205918 A, JP 2008-234909 A, JP2008-218326 A, WO 2008/099557 A1, WO 2007/141913 A1, US 2002/0041995 A1,US 2002/0041995 A1, JP 2002-117852 A, EP 1 128 453 A2 disclose polymericcompounds having organic nitroxide radicals as active units for chargestorage; US 2002/0041995, JP 2002-117852 A disclose, by way of example,polymeric compounds having organic phenoxy radicals or galvinoxyradicals).

Other known active twits for charge storage means are polymericcompounds having quinones (for example JP 2009-217992 A, WO 2013/099567,WO 2011/068217 A1), having diones (such as JP 2010-212152 A), and havingdicyanodiimines (for example JP 2012-190545 A, JP 2010-55923 A).

As described, there has been no use to date of the11,11,12,12-tetracyanoanthraquinodimethane polymers, which are known tothe specialist field, for energy storage means, for the reasonsmentioned above.

The theoretical capacity of the already known polymers havingredox-active substituents is strictly limited by two factors: firstly bythe molar mass of the monomer unit and secondly by the number ofelectrons involved in the redox reaction of the electrical chargestorage. Most organic redox active units have only a one-electronprocess which is used for charge storage and therefore, as noted above,have a low theoretical capacity because of their comparatively highmolar mass.

The use of multi-electron redox processes, as is the case, for example,for quinones or dicyanodiimides, increases the theoretical capacity ofthe material, but these multi-electron processes are interdependent, andso the redox reactions take place at different potentials and henceseveral unwanted charging/discharging plateaus arise at different cellvoltages in the respective electrical charge storage means.

SUMMARY OF THE INVENTION

The problem on which the invention is based is therefore that ofproviding novel polymers which are preparable with a low level ofcomplexity, with the possibility of controlled influence on thephysicochemical properties thereof within wide limits in the course ofsynthesis, and which can be used as active materials in electricalcharge storage means for high storage capacity, long lifetime and a flatcharging/discharging plateau.

Novel tetracyanoanthraquinodimethane polymers consisting of anoligomeric or polymeric compound of the general formula I have beenfound:

where

-   -   R₁ to R₇: may preferably each independently be hydrogen atoms,        alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups,        alkylthio groups, haloalkyl groups, haloalkoxy groups,        cycloalkyl groups, cycloalkoxy groups, acyl groups, heteroaryl        groups, aryloxy groups, aralkyl groups, carboxylic acid groups,        sulphonic acid groups, amino groups, monoalkylamino groups,        dialkylamino groups, nitro groups, cyano groups, hydroxyl        groups, alkylcarbonyl groups, alkenylcarbonyl groups,        alkynylcarbonyl groups, carboxylic ester groups, carboxamide        groups, sulphonic ester groups, thiol groups, halogen atoms or a        combination of these groups or atoms, particular preference        being given to hydrogen atoms as at least five of the R₁ to R₇        substituents and to non-hydrogen atoms, preferably halogen        atoms, alkyl groups, alkoxy groups, cyano groups and/or nitro        groups, as zero to two of the R₁ to R₇ substituents,    -   X: is an organic group which is formed by polymerization        reaction from a group consisting of an organic double bond, an        organic triple bond, an oxirane or an aziridine, or is an        organic group which is formed by a polymer-analogous reaction,    -   n: is an integer greater than or equal to 2.

The organic X group may preferably have a structure of the followingformulae II-XIV:

-   -   where    -   R₈ to R₂₄: may preferably each independently be hydrogen atoms,        alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups,        alkylthio groups, haloalkyl groups, haloalkoxy groups,        cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl        groups, aryloxy groups, aralkyl groups, carboxylic acid groups,        sulphonic acid groups, amino groups, monoalkylamino groups,        dialkylamino groups, nitro groups, cyano groups, hydroxyl        groups, alkylcarbonyl groups, alkenylcarbonyl groups,        alkynylcarbonyl groups, carboxylic ester groups, carboxamide        groups, sulphonic ester groups, thiol groups, halogen atoms or a        combination of these groups or atoms, particular preference        being given to        -   hydrogen atoms as at least two of the R₈ to R₁₀ substituents            and to non-hydrogen atoms, preferably halogen atoms, alkyl            groups, alkoxy groups, cyano groups and/or nitro groups, as            zero to two of the R₈ to R₁₀ substituents, and/or        -   hydrogen atoms as at least two of the R₁₁ to R₁₃            substituents and to non-hydrogen atoms, preferably halogen            atoms, alkyl groups, alkoxy groups, cyano groups and; or            nitro groups, as zero to one of the R₁₁ to R₁₃ substituents,            and/or        -   a hydrogen atom as R₁₄, and/or        -   hydrogen atoms as at least two of the R₁₅ to R₁₇            substituents and to non-hydrogen atoms, preferably halogen            atoms, alkyl groups, alkoxy groups, cyano groups and/or            nitro groups, as zero to one of the R₁₅ to R₁₇ substituents,            and/or        -   hydrogen atoms as at least two of the R₁₈ to R₂₀            substituents and to non-hydrogen atoms, preferably halogen            atoms, alkyl groups, alkoxy groups, cyano groups and/or            nitro groups, as zero to one of the R₁₈ to R₂₀ substituents,            and/or        -   a hydrogen atom as R₂₁, and/or        -   hydrogen atoms as at least two of the R₂₂ to R₂₄            substituents and to non-hydrogen atoms, preferably halogen            atoms, alkyl groups, alkoxy groups, cyano groups and/or            nitro groups, as zero to one of the R₂₂ to R₂₄ substituents,    -   R₂₆ to R₂₈: may preferably each independently be hydrogen atoms,        alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups,        alkylthio groups, haloalkyl groups, haloalkoxy groups,        cycloalkyl groups, cycloalkoxy groups, aryl groups, to        heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic        acid groups, sulphonic acid groups, amino groups, monoalkylamino        groups, dialkylamino groups, nitro groups, cyano groups,        hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups,        alkynylcarbonyl groups, carboxylic ester groups, carboxamide        groups, sulphonic ester groups, thiol groups, halogen atoms or a        combination of these groups or atoms, particular preference        being given to hydrogen atoms as at least two of the R₂₆ to R₂₈        substituents and to non-hydrogen atoms, preferably halogen        atoms, alkyl groups, alkoxy groups, cyano groups and; or nitro        groups, as zero to one of the R₂₆ to R₂₈ substituents,    -   R₃₀ to R₃₂: may preferably each independently be hydrogen atoms,        alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups,        alkylthio groups, haloalkyl groups, haloalkoxy groups,        cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl        groups, aryloxy groups, aralkyl groups, carboxylic acid groups,        sulphonic acid groups, amino groups, monoalkylamino groups,        dialkylamino groups, nitro groups, cyano groups, alkylcarbonyl        groups, alkenylcarbonyl groups, alkynylcarbonyl groups,        carboxylic ester groups, carboxamide groups, sulphonic ester        groups, halogen atoms or a combination of these groups or atoms,        particular preference being given to hydrogen atoms as at least        two of the R₃₀ to R₃₂ substituents and to non-hydrogen atoms,        preferably halogen atoms, alkyl groups, alkoxy groups, cyano        groups and/or nitro groups, as zero to one of the R₃₀ to R₃₂        substituents,    -   R₃₃ to R₃₅: may preferably each independently be hydrogen atoms,        alkyl groups, alkenyl groups, alkoxy groups, alkylthio groups,        haloalkyl groups, haloalkoxy groups, cycloalkyl groups,        cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy        groups, aralkyl groups, carboxylic acid groups, sulphonic acid        groups, amino groups, monoalkylamino groups, dialkylamino        groups, nitro groups, cyano groups, hydroxyl groups,        alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl        groups, carboxylic ester groups, carboxamide groups, sulphonic        ester groups, thiol groups, halogen atoms or a combination of        these groups or atoms, particular preference being given to        hydrogen atoms as at least two of the R₃₃ to R₃₅ substituents        and to non-hydrogen atoms, preferably halogen atoms, alkyl        groups, alkoxy groups, cyano groups and/or nitro groups, as zero        to one of the R₃₃ to R₃₅ substituents,    -   A: is an oxygen atom, a sulphur atom or an —N(R₂₉)— group, where        R₂₉ is preferably a hydrogen atom, alkyl group, alkenyl group,        alkynyl group, alkoxy group, alkylthio group, haloalkyl group,        haloalkoxy group, cycloalkyl group, cycloalkoxy group, aryl        group, heteroaryl group, aryloxy group, aralkyl group,        carboxylic acid group, sulphonic acid group, nitro group,        alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl        group, carboxylic ester group, carboxamide group, sulphonic        ester group, particular preference being given to an oxygen atom        as A,    -   A₁ and A₂: are preferably each independently a covalent bond, an        alkyl group, an alkenyl group, an alkynyl group, an alkoxy        group, an alkylthio group, a haloalkyl group, a haloalkoxy        group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a        heteroaryl group, an aryloxy group, an aralkyl group, a        monoalkylamino group, a dialkylamino group, an alkylcarbonyl        group, an alkenylcarbonyl group, an alkynylcarbonyl group, a        carboxylic ester group, a carboxamide group, a sulphonic ester        group, particular preference being given to a covalent bond or        an alkyl group as A₁ and A₂,    -   A₃ and A₄: may preferably each independently be a covalent bond,        an alkyl group, an alkenyl group, an alkynyl group, an alkoxy        group, an alkylthio group, a cycloalkyl group, a cycloalkoxy        group, an aryl group, a heteroaryl group, an aryloxy group, an        aralkyl group, a dialkylamino group, an alkylcarbonyl group, an        alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylic        ester group, a carboxamide group, a sulphonic ester group,        particular preference being given to a covalent bond or an alkyl        group as A₁ and A₂,    -   A₅ and A₆: may preferably each independently be a covalent bond,        an alkyl group, an alkenyl group, an alkoxy group, an alkylthio        group, a haloalkyl group, a haloalkoxy group, a cycloalkyl        group, a cycloalkoxy group, an aryl group, a heteroaryl group,        an aryloxy group, an aralkyl group, a monoalkylamino group, a        dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl        group, an alkynylcarbonyl group, a carboxylic ester group, a        carboxamide group, a sulphonic ester group, particular        preference being given to a covalent to bond, an aryl group or        an alkyl group as A₅ and A₆,    -   Ar: is an independently substituted cycloalkyl group,        cycloalkoxy group, aryl group, heteroaryl group, aryloxy group,        aralkyl group.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1: Cyclic voltammograms of a monomer prepared according to Example2 (broken line) and of an electrode produced therefrom according toExample 4 (solid line).

FIG. 2: Charge/discharge curves of the first (solid line) and fivehundredth (broken line) charging/discharging cycle of a secondarybattery produced according to Example 5.

FIG. 3: Charging/discharging behaviour of the secondary battery producedaccording to Example 5.

FIG. 4: Coulomb efficiency of the secondary battery′ produced accordingto Example 5.

DETAILED DESCRIPTION OF THE INVENTION

Novel polymers containing 11,11,12,12-tetracyanoanthraquinodimethaneunits as the pendant group on the polymer backbone have beensynthesized. These polymers have excellent properties, especially asredox active electrode material in anodes or cathodes for secondaryelectrical charge storage means. The dependent claims specifyadvantageous possible uses of the inventivetetracyanoanthraquinodimethane polymers.

These novel polymers can be prepared in a simple and uncomplicatedmanner, and from readily obtainable starting materials. No furthermonomer is needed for the polymerization, and the polymerization doesnot require any costly metal catalysts; instead, it is possible to usesimple polymerization processes as the production method. At the sametime, it is possible to obtain polymers having a high molar mass and lowpolydispersity index in very high yields. The introduction ofpolymerizable groups of low molar mass makes it possible to keep themolar mass of the monomer low and to maximize the theoretical capacityof the secondary electrical charge storage means. In addition, the redoxactive groups in these polymers are not conjugated to one another; as aconsequence, the electrical charge storage means has a flatcharging/discharging plateau. These materials differ from the prior artby a two-electron redox reaction which leads to said flatcharging/discharging plateau, combined with simultaneously high capacityand long lifetime in the component.

In the description which follows, n is defined as normal, i as iso, s assecondary, t as tertiary, c as cyclo, m as meta, p as para and o asortho.

In this specification, an alkyl group may be either branched orunbranched. An alkyl group typically consists of one up to thirty carbonatoms, preferably of one up to twenty carbon atoms. Examples of an alkylgroup are: methyl group, ethyl group, propyl group, isopropyl group,n-butyl group, sec-butyl group, t-butyl group, pentyl group, n-hexylgroup, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group,n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group,n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecylgroup, n-octadecyl group, n-nonadecyl group or eicosyl group. Particularpreference is given to alkyl groups having one to six carbon atoms.

In this specification, an alkenyl group may be either branched orunbranched. An alkenyl group typically consists of one up to thirtycarbon atoms, preferably of one up to twenty carbon atoms. Alkenylgroups typically have one unsaturated ethenylic double bond; theremaining proportion of the alkenyl group is saturated. Two or moreethenylic unsaturated double bonds are possible but not preferred. Theunsaturated ethenylic double bond is more preferably at the alphaposition in the alkenyl group. Examples of an alkenyl group are: vinylgroup, allyl group, propenyl group, isopropenyl group, n-butenyl group,sec-butenyl group, pentenyl group, n-hexenyl group, n-heptenyl group,2-ethylhexenyl group, n-octenyl group, n-nonenyl group, n-decenyl group,n-undecenyl group, n-dodecenyl group, n-tridecenyl group, n-tetradecenylgroup, n-pentadecenyl group, n-hexadecenyl group, n-heptadecenyl group,n-octadecenyl group, n-nonadecenyl group or eicosenyl group. Preferenceis given to alkenyl groups having two to three carbon atoms; particularpreference is given to vinyl groups and allyl groups.

In this specification, an alkynyl group may be either branched orunbranched. An alkynyl group typically consists of two up to thirtycarbon atoms, preferably of one up to twenty carbon atoms. Alkynylgroups typically have one unsaturated ethynylic triple bond; theremaining proportion of the alkynyl group is saturated. Two or moreethynylic unsaturated triple bonds are possible but not preferred. Theunsaturated ethynylic double bond is more preferably at the alphaposition in the alkynyl group. Examples of an alkynyl group are: ethynylgroup, propynyl group, butynyl group, pentynyl group, n-hexynyl group,n-heptynyl group, 2-ethylhexynyl group, n-octynyl group, n-nonynylgroup, n-decynyl group, n-undecynyl group, n-dodecynyl group,n-tridecynyl group, n-tetradecynyl group, n-pentadecynyl group,n-hexadecynyl group, n-heptadecynyl group, n-octadecynyl group,n-nonadecynyl group or eicosynyl group. Preference is given to alkynylgroups having two carbon atoms.

In this specification, an alkylthio group may be either branched orunbranched. An alkylthio group typically consists of one up to thirtycarbon atoms and one or more sulphur atoms bonded covalently to twocarbon atoms in the chain, preferably of one to twenty to carbon atomsand one sulphur atom. Examples of an alkylthio group are: methylthiogroup, ethylthio group, n-propylthio group, i-propylthio group,n-butylthio group, s-butylthio group, t-butylthio group, n-pentylthiogroup, 1-methylbutylthio group, 2-methylbutylthio group,3-methylbutylthio group, 1,1-dimethylpropylthio group,2,2-dimethylpropylthio group, n-hexylthio group, 1-methylpentylthiogroup, 2-methylpentylthio group, 1,1-dimethylbutylthio group,1-ethylbutylthio group, 1,1,2-trimethylpropylthio group, n-heptylthiogroup, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group,n-decylthio group, n-dodecylthio group.

In this specification, a monoalkylamino group may be either branched orunbranched. A monoalkylamino group typically consists of one up tothirty carbon atoms and one or more nitrogen atoms bonded covalently totwo carbon atoms in the chain, preferably of one to twenty carbon atomsand one nitrogen atom. Examples of a monoalkylamino group are:methylamino group, ethylamino group, n-propylamino group, i-propylaminogroup, c-propylamino group, n-butylamino group, i-butylamino group,s-butylamino group, 1-butylamino group, c-butylamino group,1-methyl-c-propylamino group, 2-methyl-c-propylamino group,n-pentylamino group, 1-methyl-n-butylamino group, 2-methyl-n-butylaminogroup, 3-methyl-n-butylamino group, 1,1-dimethyl-n-propylamino group,1,2-dimethyl-n-propylamino group, 2,2-dimethyl-n-propylamino group,1-ethyl-n-propylamino group, c-pentylamino group, 1-methyl-c-butylaminogroup, 2-methyl-c-butylamino group, 3-methyl-c-butylamino group,1,2-dimethyl-c-propylamino group, 2,3-dimethyl-c-propylamino group,1-ethyl-c-propylamino group, 2-ethyl-c-propylamino group, n-hexylaminogroup, 1-methyl-n-pentylamino group, 2-methyl-n-pentylamino group,3-methyl-n-pentylamino group, 4-methyl-n-pentylamino group,1,1-dimethyl-n-butylamino group, 1,2-dimethyl-n-butylamino group,1,3-dimethyl-n-butylamino group, 2,2-dimethyl-n-butylamino group,2,3-dimethyl-n-butylamino group, 3,3-dimethyl-n-butylamino group,1-ethyl-n-butylamino group, 2-ethyl-n-butylamino group,1,1,2-trimethyl-n-propylamino group, 1,2,2-trimethyl-n-propylaminogroup, 1-ethyl-1-methyl-n-propylamino group,1-ethyl-2-methyl-n-propylamino group, c-hexylamino group,1-methyl-c-pentylamino group, 2-methyl-c-pentylamino group,3-methyl-c-pentylamino group, 1-ethyl-c-butylamino group,2-ethyl-c-butylamino group, 3-ethyl-c-butylamino group,1,2-dimethyl-c-butylamino group, 1,3-dimethyl-c-butylamino group,2,2-dimethyl-c-butylamino group, to 2,3-dimethyl-c-butylamino group,2,4-dimethyl-c-butylamino group, 3,3-dimethyl-c-butylamino group,1-n-propyl-c-propylamino group, 2-n-propyl-c-propylamino group,1-i-propyl-c-propylamino group, 2-i-propyl-c-propylamino group,1,2,2-trimethyl-c-propylamino group, 1,2,3-trimethyl-c-propylaminogroup, 2,2,3-trimethyl-c-propylamino group,1-ethyl-2-methyl-c-propylamino group, 2-ethyl-1-methyl-c-propylaminogroup, 2-ethyl-2-methyl-c-propylamino group,2-ethyl-3-methyl-c-propylamino group.

In this specification, a dialkylamino group may be either branched orunbranched. A dialkylamino group typically consists of one up to thirtycarbon atoms and one or more nitrogen atoms bonded covalently to threecarbon atoms in the chain, preferably of one to twenty carbon atoms andone nitrogen atom. Examples of a dialkylamino group are:di-i-propylamino group, di-c-propylamino group, di-n-butylamino group,di-i-butylamino group, di-s-butylamino group, di-t-butylamino group,di-c-butylamino group, di(1-methyl-c-propyl)amino group,di(2-methyl-c-propyl)amino group, di-n-pentylamino group,di(1-methyl-n-butylamino group, di(2-methyl-n-butyl)amino group,di(3-methyl-n-butyl)amino group, di(1,1-dimethyl-n-propyl)amino group,di(1,2-dimethyl-n-propyl)amino group, di(2,2-dimethyl-n-propyl)aminogroup, di(1-ethyl-n-propyl)amino group, di-c-pentylamino group,di(1-methyl-c-butyl)amino group, di(2-methyl-c-butyl)amino group,di(3-methyl-c-butyl)amino group, di(1,2-dimethyl-c-propyl)amino group,di(2,3-dimethyl-c-propyl)amino group, di(1-ethyl-c-propyl)amino group,di(2-ethyl-c-propyl)amino group, di-n-hexylamino group,di(1-methyl-n-pentyl)amino group, di(2-methyl-n-pentyl)amino group,di(3-methyl-n-pentyl)amino group, di(4-methyl-n-pentyl)amino group,di(1,1-dimethyl-n-butyl)amino group, di(1,2-dimethyl-n-butyl)aminogroup, di(1,3-dimethyl-n-butyl)amino group.

In this specification, a haloalkyl group may be either branched orunbranched. A haloalkyl group typically consists of one up to thirtycarbon atoms which may in turn each independently be substituted by oneor more halogen atoms, preferably of one to twenty carbon atoms.Examples of halogen atoms are the fluorine atom, chlorine atom, bromineatom and iodine atom. Preference is given to the fluorine atom and thechlorine atom. Examples of a haloalkyl group are: difluoromethoxy group,trifluoromethoxy group, to bromodifluoromethoxy group, 2-chloroethoxygroup, 2-bromoethoxy group, 1,1-difluoroethoxy group,2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group,2-chloro-1,1,2-trifluoroethoxy group, pentafluoroethoxy group,3-bromopropoxy group, 2,2,3,3-tetrafluoropropoxy group,1,1,2,3,3,3-hexafluoropropoxy group, 1,1,1,3,3,3-hexafluoropropoxygroup, 3-bromo-2-methylpropoxy group, 4-bromobutoxy group,perfluoropentyloxy group.

In this specification, a haloalkoxy group may be either branched orunbranched. A haloalkoxy group typically consists of an oxygen atom witha chain consisting of one up to thirty carbon atoms covalently bondedthereto, which may be either branched or unbranched, and wherein thecarbon atoms may in turn each independently be substituted by one ormore halogen atoms. This chain preferably consists of one to twentycarbon atoms. Examples of halogen atoms are the fluorine atom, chlorineatom, bromine atom and iodine atom. Preference is given to the fluorineatom and the chlorine atom. Examples of a haloalkoxy group are:difluoromethoxy group, trifluoromethoxy group, bromodifluoromethoxygroup, 2-chloroethoxy group, 2-bromoethoxy group, 1,1-difluoroethoxygroup, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group,2-chloro-1,1,2-trifluoroethoxy group, pentafluoroethoxy group,3-bromopropoxy group, 2,2,3,3-tetrafluoropropoxy group,1,1,2,3,3,3-hexafluoropropoxy group, 1,1,1,3,3,3-hexafluoropropoxygroup, 3-bromo-2-methylpropoxy group, 4-bromobutoxy group,perfluoropentoxy group.

An alkylcarbonyl group in this specification typically consists of acarbonyl carbon with an alkyl group consisting of one up to thirtycarbon atoms bonded covalently thereto, which may be either branched orunbranched. This chain preferably consists of one to twenty carbonatoms. Examples of an alkylcarbonyl group are: methylcarbonyl group,ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group,c-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group,s-butylcarbonyl group, t-butylcarbonyl group, c-butylcarbonyl group,1-methyl-c-propylcarbonyl group, 2-methyl-c-propylcarbonyl group,n-pentylcarbonyl group, 1-methyl-n-butylcarbonyl group,2-methyl-n-butylcarbonyl group, 3-methyl-n-butylcarbonyl group,1,1-dimethyl-n-propylcarbonyl group, 1,2-dimethyl-n-propylcarbonylgroup, 2,2-dimethyl-n-propylcarbonyl group, 1-ethyl-n-propylcarbonylgroup, c-pentylcarbonyl group, 1-methyl-c-butylcarbonyl group,2-methyl-c-butylcarbonyl group, 3-methyl-c-butylcarbonyl group,1,2-dimethyl-c-propylcarbonyl group, 2,3-dimethyl-c-propylcarbonylgroup, 1-ethyl-c-propylcarbonyl group, 2-ethyl-c-propylcarbonyl group,n-hexylcarbonyl group, 1-methyl-n-pentylcarbonyl group,2-methyl-n-pentylcarbonyl group, 3-methyl-n-pentylcarbonyl group,4-methyl-n-pentylcarbonyl group, 1,1-dimethyl-n-butylcarbonyl group,1,2-dimethyl-n-butylcarbonyl group, 1,3-dimethyl-n-butylcarbonyl group,2,2-dimethyl-n-butylcarbonyl group, 2,3-dimethyl-n-butylcarbonyl group,3,3-dimethyl-n-butylcarbonyl group, 1-ethyl-n-butylcarbonyl group,2-ethyl-n-butylcarbonyl group.

An alkenylcarbonyl group in this specification typically consists of acarbonyl carbon with an alkenyl group consisting of one up to thirtycarbon atoms bonded covalently thereto, which may be either branched orunbranched. This chain preferably consists of one to twenty carbonatoms. Examples of an alkenylcarbonyl group are: ethenylcarbonyl group,1-propenylcarbonyl group, 2-propenylcarbonyl group,1-methyl-1-ethenylcarbonyl group, 1-butenylcarbonyl group,2-butenylcarbonyl group, 3-butenylcarbonyl group,2-methyl-1-propenylcarbonyl group, 2-methyl-2-propenylcarbonyl group,1-ethylethenylcarbonyl group, 1-methyl-1-propenylcarbonyl group,1-methyl-2-propenylcarbonyl group, 1-pentenylcarbonyl group,2-pentenylcarbonyl group, 3-pentenylcarbonyl group, 4-pentenylcarbonylgroup, 1-n-propylethenylcarbonyl group, 1-methyl-1-butenylcarbonylgroup, 1-methyl-2-butenylcarbonyl group, 1-methyl-3-butenylcarbonylgroup, 2-ethyl-2-propenylcarbonyl group, 2-methyl-1-butenylcarbonylgroup, 2-methyl-2-butenylcarbonyl group, 2-methyl-3-butenylcarbonylgroup, 3-methyl-1-butenylcarbonyl group, 3-methyl-2-butenylcarbonylgroup, 3-methyl-3-butenylcarbonyl group, 1,1-dimethyl-2-propenylcarbonylgroup, 1-i-propyl ethenyl carbonyl group,1,2-dimethyl-1-propenylcarbonyl group, 1,2-dimethyl-2-propenylcarbonylgroup, 1-c-pentenylcarbonyl group, 2-c-pentenylcarbonyl group,3-c-pentenylcarbonyl group, 1-hexenylcarbonyl group, 2-hexenylcarbonylgroup, 3-hexenylcarbonyl group, 4-hexenylcarbonyl group,5-hexenylcarbonyl group, 1-methyl-1-pentenylcarbonyl group,1-methyl-2-pentenylcarbonyl group, 1-methyl-3-pentenylcarbonyl group,1-methyl-4-pentenylcarbonyl group, 1-n-butylethenylcarbonyl group,2-methyl-1-pentenylcarbonyl group, 2-methyl-2-pentenylcarbonyl group,2-methyl-3-pentenylcarbonyl group, 2-methyl-4-pentenylcarbonyl group,2-n-propyl-2-propenylcarbonyl group, 3-methyl-1-pentenylcarbonyl group,3-methyl-2-pentenylcarbonyl group.

An alkynylcarbonyl group in this specification typically consists of acarbonyl carbon with an alkynyl group consisting of one up to thirtycarbon atoms bonded covalently thereto, which may be either branched orunbranched. This chain preferably consists of one to twenty carbonatoms. Examples of an alkynylcarbonyl group are: ethynylcarbonyl group,1-propynylcarbonyl group, 2-propynylcarbonyl group, 1-butynylcarbonylgroup, 2-butynylcarbonyl group, 3-butynylcarbonyl group,1-methyl-2-propynylcarbonyl group, 1-pentynylcarbonyl group,2-pentynylcarbonyl group, 3-pentynylcarbonyl group, 4-pentynylcarbonylgroup, 1-methyl-2-butynylcarbonyl group, 1-methyl-3-butynylcarbonylgroup, 2-methyl-3-butynylcarbonyl group, 3-methyl-1-butynylcarbonylgroup, 1,1-dimethyl-2-propynylcarbonyl group, 2-ethyl-2-propynylcarbonylgroup, 1-hexynylcarbonyl group, 2-hexynylcarbonyl group,3-hexynylcarbonyl group, 4-hexynylcarbonyl group, 5-hexynylcarbonylgroup, 1-methyl-2-pentynylcarbonyl group, 1-methyl-3-pentynylcarbonylgroup, 1-methyl-4-pentynylcarbonyl group, 2-methyl-3-pentynylcarbonylgroup, 2-methyl-4-pentynylcarbonyl group, 3-methyl-1-pentynylcarbonylgroup, 3-methyl-4-pentynylcarbonyl group, 4-methyl-1-pentynylcarbonylgroup, 4-methyl-2-pentynylcarbonyl group, 1,1-dimethyl-2-butynylcarbonylgroup, 1,1-dimethyl-3-butynylcarbonyl group,1,2-dimethyl-3-butynylcarbonyl group, 2,2-dimethyl-3-butynylcarbonylgroup, 3,3-dimethyl-1-butynylcarbonyl group, 1-ethyl-2-butynylcarbonylgroup, 1-ethyl-3-butynylcarbonyl group.

An alkylcarboxylic ester group in this specification typically consistsof a carboxylic ester with an alkyl group consisting of one up to thirtycarbon atoms bonded covalently thereto, which may be either branched orunbranched. This chain preferably consists of one to twenty carbonatoms. Examples of an alkylcarboxylic ester group are: methylcarboxylicester group, ethylcarboxylic ester group, n-propylcarboxylic estergroup, i-propylcarboxylic ester group, c-propylcarboxylic ester group,n-butylcarboxylic ester group, i-butylcarboxylic ester group,s-butylcarboxylic ester group, 1-butylcarboxylic ester group,c-butylcarboxylic ester group, 1-methyl-c-propylcarboxylic ester group,2-methyl-c-propylcarboxylic ester group, n-pentylcarboxylic ester group,1-methyl-n-butylcarboxylic ester group, 2-methyl-n-butylcarboxylic estergroup, 3-methyl-n-butylcarboxylic ester group,1,1-dimethyl-n-propylcarboxylic ester group,1,2-dimethyl-n-propylcarboxylic ester group,2,2-dimethyl-n-propylcarboxylic ester group, 1-ethyl-n-propylcarboxylicester group, c-pentylcarboxylic ester group, 1-methyl-c-butylcarboxylicester group, 2-methyl-c-butylcarboxylic ester group,3-methyl-c-butylcarboxylic ester group, 1,2-dimethyl-c-propylcarboxylicester group, 2,3-dimethyl-c-propylcarboxylic ester group,1-ethyl-c-propylcarboxylic ester group, 2-ethyl-c-propylcarboxylic estergroup, n-hexylcarboxylic ester group, 1-methyl-n-pentylcarboxylic estergroup, 2-methyl-n-pentylcarboxylic ester group,3-methyl-n-pentylcarboxylic ester group, 4-methyl-n-pentylcarboxylicester group, 1,1-dimethyl-n-butylcarboxylic ester group,1,2-dimethyl-n-butylcarboxylic ester group,1,3-dimethyl-n-butylcarboxylic ester group,2,2-dimethyl-n-butylcarboxylic ester group,2,3-dimethyl-n-butylcarboxylic ester group,3,3-dimethyl-n-butylcarboxylic ester group, 1-ethyl-n-butylcarboxylicester group, 2-ethyl-n-butylcarboxylic ester group.

An alkenylcarboxylic ester group in this specification typicallyconsists of a carboxylic ester with an alkenyl group consisting of oneup to thirty carbon atoms bonded covalently thereto, which may be eitherbranched or unbranched. This chain preferably consists of one to twentycarbon atoms. Examples of an alkenylcarboxylic ester group are:ethenylcarboxylic ester group, 1-propenylcarboxylic ester group,2-propenylcarboxylic ester group, 1-methyl-1-ethenylcarboxylic estergroup, 1-butenylcarboxylic ester group, 2-butenylcarboxylic ester group,3-butenylcarboxylic ester group, 2-methyl-1-propenylcarboxylic estergroup, 2-methyl-2-propenylcarboxylic ester group,1-ethylethenylcarboxylic ester group, 1-methyl-1-propenylcarboxylicester group, 1-methyl-2-propenylcarboxylic ester group,1-pentenylcarboxylic ester group, 2-pentenylcarboxylic ester group,3-pentenylcarboxylic ester group, 4-pentenylcarboxylic ester group,1-n-propylethenylcarboxylic ester group, 1-methyl-1-butenylcarboxylicester group, 1-methyl-2-butenylcarboxylic ester group,1-methyl-3-butenylcarboxylic ester group, 2-ethyl-2-propenylcarboxylicester group, 2-methyl-1-butenylcarboxylic ester group,2-methyl-2-butenylcarboxylic ester group, 2-methyl-3-butenylcarboxylicester group, 3-methyl-1-butenylcarboxylic ester group,3-methyl-2-butenylcarboxylic ester group, 3-methyl-3-butenylcarboxylicester group, 1,1-dimethyl-2-propenylcarboxylic ester group,1-i-propylethenylcarboxylic ester group,1,2-dimethyl-1-propenylcarboxylic ester group,1,2-dimethyl-2-propenylcarboxylic ester group, 1-c-pentenylcarboxylicester group, 2-c-pentenylcarboxylic ester group, 3-c-pentenylcarboxylicester group, 1-hexenylcarboxylic ester group, 2-hexenylcarboxylic estergroup, 3-hexenylcarboxylic ester group, 4-hexenylcarboxylic ester group,5-hexenylcarboxylic ester group, 1-methyl-1-pentenylcarboxylic estergroup, 1-methyl-2-pentenylcarboxylic ester group,1-methyl-3-pentenylcarboxylic ester group, 1-methyl-4-pentenylcarboxylicester group, 1-n-butylethenylcarboxylic ester group,2-methyl-1-pentenylcarboxylic ester group, 2-methyl-2-pentenylcarboxylicester group, 2-methyl-3-pentenylcarboxylic ester group,2-methyl-4-pentenylcarboxylic ester group,2-n-propyl-2-propenylcarboxylic ester group,3-methyl-1-pentenylcarboxylic ester group, 3-methyl-2-pentenylcarboxylicester group.

An alkynylcarboxylic ester group in this specification typicallyconsists of a carboxylic ester with an alkynyl group consisting of oneup to thirty carbon atoms bonded covalently thereto, which may be eitherbranched or unbranched. This chain preferably consists of one to twentycarbon atoms. Examples of an alkynylcarboxylic ester group are:ethynylcarboxylic ester group, 1-propynylcarboxylic ester group,2-propynylcarboxylic ester group, 1-butynylcarboxylic ester group,2-butynylcarboxylic ester group, butynylcarboxylic ester group,1-methyl-2-propynylcarboxylic ester group, 1-pentynylcarboxylic estergroup, 2-pentynylcarboxylic ester group, 3-pentynylcarboxylic estergroup, 4-pentynylcarboxylic ester group, 1-methyl-2-butynylcarboxylicester group, 1-methyl-3-butynylcarboxylic ester group,2-methyl-butynylcarboxylic ester group, methyl-1-butynylcarboxylic estergroup, 1,1-dimethyl-2-propynylcarboxylic ester group,2-ethyl-2-propynylcarboxylic ester group, 1-hexynylcarboxylic estergroup, 2-hexynylcarboxylic ester group, 3-hexynylcarboxylic ester group,4-hexynylcarboxylic ester group, 5-hexynylcarboxylic ester group,1-methyl-2-pentynylcarboxylic ester group, 1-methyl-3-pentynylcarboxylicester group, 1-methyl-4-pentynylcarboxylic ester group,2-methyl-3-pentynylcarboxylic ester group, 2-methyl-4-pentynylcarboxylicester group, 3-methyl-1-pentynylcarboxylic ester group,3-methyl-4-pentynylcarboxylic ester group, 4-methyl-1-pentynylcarboxylicester group, 4-methyl-2-pentynylcarboxylic ester group,1,1-dimethyl-2-butynylcarboxylic ester group,1,1-dimethyl-3-butynylcarboxylic ester group,1,2-dimethyl-3-butynylcarboxylic ester group,2,2-dimethyl-3-butynylcarboxylic ester group,3,3-dimethyl-1-butynylcarboxylic ester group,1-ethyl-2-butynylcarboxylic ester group, 1-ethyl-3-butynylcarboxylicester group.

In this specification, an alkoxy group may consist of an alkyl unitwhich may be either branched or unbranched. An alkoxy group typicallyconsists of one to thirty carbon atoms, preferably of one to twentycarbon atoms. Examples of an alkoxy group are: methoxy group, ethoxygroup, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxygroup, pentyloxy group, n-hexyloxy group, n-heptyloxy group,2-ethylhexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxygroup, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxygroup, n-hexadecyloxy group, n-octadecyloxy group or eicosyloxy group.Preference is given to alkoxy groups having one up to six carbon atomsin the alkyl unit.

A cycloalkyl group as described in this specification is typically acyclic group consisting of five, six or seven carbon atoms, each ofwhich may independently be substituted. Examples of substituents arealkyl groups, or two alkyl groups which, together with the ring carbonsto which they are bonded, form a further ring. One example of acycloalkyl group is a cyclohexyl group.

A cycloalkoxy group as described in this specification is typically acyclic group consisting of five, six or seven carbon atoms, of which atleast one is bonded covalently to an oxygen atom. These ring carbonatoms may each independently be substituted, for example by alkylgroups, or two alkyl groups which, together with the ring carbons towhich they are bonded, form a further ring. One example of a cycloalkoxygroup is a cyclohexyloxy group.

An aryl group as described in this specification is typically a cyclicaromatic group consisting of five to ten carbon atoms, each of which mayindependently be substituted. Examples of substituents are alkyl groups,or two alkyl groups which, together with the ring carbons to which theyare bonded, form a further ring. Examples of an aryl group are phenylgroup, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group,1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenantolyl group,2-phenantolyl group, 3-phenantolyl group, 4-phenantolyl group,9-phenantolyl group.

A heteroaryl group as described in this specification is typically acyclic aromatic group consisting of four to ten carbon atoms and atleast one heteroatom, each of which may independently be substituted.Examples of substituents are alkyl groups, or two alkyl groups which,together with the ring carbons to which they are bonded, form a furtherring. Examples of heteroatoms in this context are an oxygen atom,nitrogen atom, phosphorus atom, boron atom, selenium atom or sulphuratom. Examples of a heteroaryl group are furyl group, thienyl group,pyrrolyl group or imidazolyl group.

An aryloxy group as described in this specification is typically an arylgroup, where aryl has already been defined above, bonded covalently toan oxygen atom. Examples of an aryloxy group are phenyloxy ornaphthyloxy.

An aralkyl group as described in this specification is typically an arylgroup, where aryl has already been defined above, bonded covalently toan alkyl group. This group may, for example, be substituted by alkylgroups or halogen atoms. One example of an aralkyl group is benzyl.

The average molar mass (M_(n)) of the oligomeric or polymeric compoundof this invention is in the range of 660 to 3 300 000 g/mol, preferablyin the range from 1650 to 1 650 000 g/mol, more preferably in the rangefrom 3300 to 330 000 g/mol. The average molar mass is determined bymeans of size exclusion chromatography (polystyrene standard).

In general, the oligomeric or polymeric compound of the inventivegeneral formula I of this invention consists of 2 and 5000 repeat units,preferably of 10 to 1000 repeat units.

The oligomeric or polymeric compounds of the inventive general formula Iof this invention may be either homopolymers or copolymers. Homopolymersare polymers which have been synthesized only from one monomer.Copolymers are polymers which have been synthesized from two or morepolymers. If two or more monomers are used in the synthesis, themonomers of the repeat units of the oligomeric or polymeric compound ofthis invention may be present in the oligomeric or polymeric compound inrandom distribution, as blocks or in alternation. The oligomeric orpolymeric compounds of this invention may either be in linear orcrosslinked form. Crosslinking can be effected, for example, viacopolymerization with a small proportion of an organic molecule havingtwo polymerizable groups, preferably a more highly functionalizedmonomer.

The oligomeric or polymeric compounds of the inventive general formula Iare synthesized by the polymerization of an11,11,12,12-tetracyanoanthraquinodimethane compound of the generalformula I′

X′ here is preferably an organic polymerizable group typicallyconsisting of an organic double bond, or an organic triple bond, or anoxirane or an aziridine. Particular preference is given to organicpolymerizable groups shown in the formulae II′ to VIII′.

with the definitions already described above again for R₈ to R₂₄, A andAr.

An 11,11,12,12-tetracyanoanthraquinodimethane compound of the generalformula I′ can be prepared by the combination of known reactions.

The preparation of the compound of the general formula I′ is shown inSchemes 1-7 below, but is not restricted thereto.

Methods known per se are sufficient for synthesis of the compound of theabovementioned general formula I′ according to the above Schemes 1-7.

If X′ in the general formula I′ corresponds to the abovementionedformula II′, the compound of the formula I′ can be synthesized by aknown method of polystyrene synthesis and derivatives thereof.Preferably, the abovementioned compound I′ is synthesized by radicalpolymerization, for example free-radical polymerization, but also acontrolled radical polymerization method, for example reversibleaddition-fragmentation chain transfer polymerization (RAFT), atomtransfer radical polymerization (ATRP) or nitroxide-mediatedpolymerization (NMP), within a temperature range from −30 to 150° C.,advantageously within a temperature range from 40 to 120° C., in asolvent and in a reaction time of 0.1 to 100 hours, using an initiator,for example azo compounds or peroxides, preferably benzoyl peroxide or2,2′-azobisisobutyronitrile. There are barely any restrictions forsolvents used. Preference is given to organic solvents, for exampleN,N′-dimethylformamide, N,N′-dimethylacetamide, dimethyl sulphoxide,N-methylpyrrolidone, dichloromethane, 1,2-dichloroethane, toluene,xylene, chlorobenzene or o-dichlorobenzene.

Likewise preferably, the abovementioned compound V is synthesized bycationic polymerization within a temperature range from −30 to 150° C.,advantageously within a temperature range from −20 to 50° C., in asolvent and a reaction time of 0.1 to 100 hours, using a catalyst, forexample Lewis acids or protic acids, preferably sulphuric acid, nitricacid, perchloric acid, boron trifluoroetherate complex, aluminiumtrichloride, tin tetrachloride or titanium tetrachloride. There arebarely any restrictions for solvents used. Preference is given toorganic solvents, for example N,N′-dimethylformamide,N,N′-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, tetrahydrofuran, 1,4-dioxolane, 1,2-dichloroethane,toluene, xylene, chlorobenzene or o-dichlorobenzene.

Likewise preferably, the abovementioned compound I′ is synthesized byanionic polymerization within a temperature range from −78 to 150° C.,advantageously within a temperature range from −50 to 50° C., in asolvent and a reaction time of 0.1 to 100 hours, using a catalyst, forexample Lewis bases or bases, preferably metal amides such as sodiumamide and LiC₂H₅, alkoxides such as methoxide or ethoxide, hydroxidessuch as sodium hydroxide or potassium hydroxide, cyanides, phosphines,amines or organometallic compounds, for example n-butyllithium orvinylmagnesium bromide. There are barely any restrictions for solventsused. Preference is given to organic solvents, for exampletetrahydrofuran, 1,4-dioxolane, diethyl ether, tert-butyl methyl ether,toluene, xylene, chlorobenzene or o-dichlorobenzene.

Likewise preferably, the abovementioned compound I′ is synthesized byanionic group transfer polymerization within a temperature range from−30 to 150° C., advantageously within a temperature range from −20 to50° C., in a solvent and a reaction time of 0.1 to 100 hours, using aninitiator, for example a silyl ketene acetal, and using a catalyst, forexample inorganic salts, preferably fluorides, azides or cyanides, orLewis acids, preferably zinc chloride or dialkylaluminum chloride. Thereare barely any restrictions for solvents used. Preference is given toorganic solvents, for example N,N′-dimethylformamide,N,N′-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxolane,diethyl ether, tert-butyl methyl ether, toluene, xylene, chlorobenzeneor o-dichlorobenzene.

If X′ in the general formula I′ corresponds to the abovementionedformula III′, the compound of the formula I′ can be synthesized by aknown method of polyvinyl ether synthesis and derivatives thereof.Preferably, the abovementioned compound I′ is synthesized by cationicpolymerization within a temperature range from −30 to 150° C.,advantageously within a temperature range from −20 to 50° C., in asolvent and a reaction time of 0.1 to 100 hours, using a catalyst, forexample Lewis acids or protic acids, preferably sulphuric acid, nitricacid, perchloric acid, boron trifluoroetherate complex, aluminiumtrichloride, tin tetrachloride or titanium tetrachloride.

There are barely any restrictions for solvents used. Preference is givento organic solvents, for example N,N′-dimethylformamide,N,N′-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, tetrahydrofuran, 1,4-dioxolane, 1,2-dichloroethane,toluene, xylene, chlorobenzene or o-dichlorobenzene.

If X′ in the general formula I′ corresponds to the abovementionedformula IV, the compound of the formula I′ can be synthesized by a knownmethod of polyacetylene synthesis and derivatives thereof. Preferably,the abovementioned compound F is synthesized by metal-catalysedpolymerization within a temperature range from −30 to 150° C.,advantageously within a temperature range from 0 to 100° C., in asolvent and a reaction time of 0.1 to 100 hours, using a catalyst, forexample a Wilkinson catalyst, a Ziegler-Natta catalyst, a Luttingercatalyst, a molybdenum complex, a tungsten complex, a rhodium complex,or an electrochemical polymerization method using nickel bromide.

There are barely any restrictions for solvents used. Preference is givento organic solvents, for example N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, 1,2-dichloroethane, toluene, xylene, chlorobenzene oro-dichlorobenzene.

If X′ in the general formula corresponds to the abovementioned formulaV′, the compound of the formula I′ can be synthesized by a known methodof polyacrylate synthesis and derivatives thereof. Preferably, theabovementioned compound I′ is synthesized by free-radicalpolymerization, but also controlled radical polymerization methods, forexample reversible addition-fragmentation chain transfer polymerization(RAFT), atom transfer radical polymerization (ATRP), cobalt-mediatedradical polymerization (CMRP) or nitroxide-mediated polymerization(NMP), within a temperature range from −30 to 150° C., advantageouslywithin a temperature range from 40 to 120° C., in a solvent and in areaction time of 0.1 to 100 hours, using an initiator, for example azocompounds or peroxides, preferably benzoyl peroxide or2,2′-azobisisobutyronitrile.

There are barely any restrictions for solvents used. Preference is givento organic solvents, for example N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, 1,2-dichloroethane, toluene, xylene, chlorobenzene oro-dichlorobenzene.

Likewise preferably, the abovementioned compound I′ is synthesized byanionic polymerization within a temperature range from −78 to 150° C.,advantageously within a temperature range from −50 to 50° C., in asolvent and a reaction time of 0.1 to 100 hours, using a catalyst, forexample Lewis bases or bases, preferably metal amides such as sodiumamide and LiC₂H₅, alkoxides such as methoxide or ethoxide, hydroxidessuch as sodium hydroxide or potassium hydroxide, cyanides, phosphines,amines or organometallic compounds, for example n-butyllithium orvinylmagnesium bromide. There are barely any restrictions for solventsused. Preference is given to organic solvents, for exampletetrahydrofuran, 1,4-dioxolane, diethyl ether, tert-butyl methyl ether,toluene, xylene, chlorobenzene or o-dichlorobenzene.

Likewise preferably, the abovementioned compound I′ is synthesized byanionic group transfer polymerization within a temperature range from−78 to 150° C., advantageously within a temperature range from −20 to50° C., in a solvent and a reaction time of 0.1 to 100 hours, using aninitiator, for example a silyl ketene acetal, and using a catalyst, forexample inorganic salts, preferably fluorides, azides or cyanides, orLewis acids, preferably zinc chloride or dialkylaluminum chloride. Thereare barely any restrictions for solvents used. Preference is given toorganic solvents, for example N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxolane,diethyl ether, tert-butyl methyl ether, toluene, xylene, chlorobenzeneor o-dichlorobenzene.

If X′ in the general formula I′ corresponds to the abovementionedformula VI′, the compound of the formula I′ can be synthesized by aknown method of polynorbornene synthesis and derivatives thereof.Preferably, the abovementioned compound I′ is synthesized bymetal-catalysed polymerization within a temperature range from −30 to150° C., advantageously within a temperature range from 0 to 100° C., ina solvent and in a reaction time of 0.1 to 100 hours, using a catalyst,for example a Grubbs catalyst, a molybdenum complex, a tungsten complexor a ruthenium complex.

There are barely any restrictions for solvents used. Preference is givento organic solvents, for example N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, 1,2-dichloroethane, tetrahydrofuran, toluene, xylene,chlorobenzene or o-dichlorobenzene.

If X′ in the general formula I′ corresponds to the abovementionedformula VII′, compound of the formula I′ can be synthesized by a knownmethod of polyethylene glycol synthesis and derivatives thereof.

Preferably, the abovementioned compound I′ is synthesized by cationicpolymerization within a temperature range from −30 to 150° C.,advantageously within a temperature range from 40 to 120° C., in asolvent and a reaction time of 0.1 to 100 hours, using a catalyst, forexample Lewis acids or protic acids, preferably sulphuric acid, nitricacid, perchloric acid, boron trifluoroetherate complex, aluminiumtrichloride, tin tetrachloride, diethylzinc/water or titaniumtetrachloride.

There are barely any restrictions for solvents used. Preference is givento organic solvents, for example N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, tetrahydrofuran, 1,4-dioxolane, 1,2-dichloroethane,toluene, xylene, chlorobenzene or o-dichlorobenzene.

Likewise preferably, the abovementioned compound I′ is synthesized byanionic polymerization within a temperature range from −78 to 150° C.,advantageously within a temperature range from −50 to 50° C., in asolvent and a reaction time of 0.1 to 100 hours, using a catalyst, forexample Lewis bases or bases, preferably metal amides such as sodiumamide and LiC₂H₅, alkoxides such as methoxide or ethoxide, hydroxidessuch as sodium hydroxide or potassium hydroxide, cyanides, phosphines,amines or organometallic compounds, for example n-butyllithium orvinylmagnesium bromide. There are barely any restrictions for solventsused. Preference is given to organic solvents, for exampletetrahydrofuran, 1,4-dioxolane, diethyl ether, tert-butyl methyl ether,toluene, xylene, chlorobenzene or o-dichlorobenzene.

If X′ in the general formula I′ corresponds to the abovementionedformula VIII′, the compound of the formula I′ can be synthesized by aknown method of polystyrene synthesis and derivatives thereof.Preferably, the abovementioned compound I′ is synthesized by radicalpolymerization, for example free-radical polymerization, but also acontrolled radical polymerization method, for example reversibleaddition-fragmentation chain transfer polymerization (RAFT), atomtransfer radical polymerization (ATRP) or nitroxide-mediatedpolymerization (NMP), within a temperature range from −30 to 150° C.,advantageously within a temperature range from 40 to 120° C., in asolvent and in a reaction time of 0.1 to 100 hours, using an initiator,for example azo compounds or peroxides, preferably benzoyl peroxide or2,2′˜azobisisobutyronitrile. There are barely any restrictions forsolvents used. Preference is given to organic solvents, for exampleN,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulphoxide,N-methylpyrrolidone, dichloromethane, 1,2-dichloroethane, toluene,xylene, chlorobenzene or o-dichlorobenzene.

Likewise preferably, the abovementioned compound I is synthesized bycationic polymerization within a temperature range from −30 to 150° C.,advantageously within a temperature range from −20 to 50° C., in asolvent and a reaction time of 0.1 to 100 hours, using a catalyst, forexample Lewis acids or protic acids, preferably sulphuric acid, nitricacid, perchloric acid, boron trifluoroetherate complex, aluminiumtrichloride, tin tetrachloride or titanium tetrachloride. There arebarely any restrictions for solvents used. Preference is given toorganic solvents, for example N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, tetrahydrofuran, 1,4-dioxolane, 1,2-dichloroethane,toluene, xylene, chlorobenzene or o-dichlorobenzene.

Likewise preferably, the abovementioned compound I′ is synthesized byanionic group transfer polymerization within a temperature range from−78 to 150° C., advantageously within a temperature range from −20 to50° C., in a solvent and a reaction time of 0.1 to 100 hours, using aninitiator, for example a silyl ketene acetal, and using a catalyst, forexample inorganic salts, preferably fluorides, azides or cyanides, orLewis acids, preferably zinc chloride or dialkylaluminum chloride. Thereare barely any restrictions for solvents used. Preference is given toorganic solvents, for example N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxolane,diethyl ether, tert-butyl methyl ether, toluene, xylene, chlorobenzeneor o-dichlorobenzene.

Likewise preferably, the abovementioned compound I′ is synthesized byanionic group transfer polymerization within a temperature range from−78 to 150° C., advantageously within a temperature range from −20 to50° C., in a solvent and a reaction time of 0.1 to 100 hours, using aninitiator, for example a silyl ketene acetal, and using a catalyst, forexample inorganic salts, preferably fluorides, azides or cyanides, orLewis acids, preferably zinc chloride or dialkylaluminum chloride. Thereare barely any restrictions for solvents used. Preference is given toorganic solvents, for example N,N′-dimethylformamide,N,N′-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, 1,2-dichloroethane, tetrahydrofuran, 1,4-dioxolane,diethyl ether, tert-butyl methyl ether, toluene, xylene, chlorobenzeneor o-dichlorobenzene.

In addition, the oligomeric or polymeric compounds of the inventivegeneral formula I are synthesized by polymer-analogous reaction of an11,11,12,12-tetracyanoanthraquinodimethane compound of the generalformula I″ with an oligomeric or polymeric compound of the generalformula P′.

where

-   -   R₁ to R₇ and R₂₆ to R₂₈: may preferably each independently be        hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups,        alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy        groups, cycloalkyl groups, cycloalkoxy groups, aryl groups,        heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic        acid groups, sulphonic acid groups, amino groups, monoalkylamino        groups, dialkylamino groups, nitro groups, cyano groups,        hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups,        alkynylcarbonyl groups, carboxylic ester groups, carboxamide        groups, sulphonic to ester groups, thiol groups, halogen atoms        or a combination of these groups or atoms, particular preference        being given to hydrogen atoms as at least five of the R₁ to R₇        substituents and to non-hydrogen atoms, preferably halogen        atoms, alkyl groups, alkoxy groups, cyano groups and/or nitro        groups, as zero to two of the R₁ bis R₇ substituents, and/or to        hydrogen atoms as at least two of the R₂₆ to R₂₈ substituents        and to non-hydrogen atoms, preferably halogen atoms, alkyl        groups, alkoxy groups, cyano groups and/or nitro groups, as zero        to one of the R₂₆ to R₂₈ substituents,    -   X″: is an electrophilic organic group which is attacked        nucleophilically by the hydroxyl group of the compound P′ and        hence forms a covalent bond between the compound I″ and P′        (preferably, X″ is an isocyanate group, a carbonyl halide group,        where the halogen is preferably chlorine, bromine or iodine, a        carboxylic acid group, a halogen atom, where the halogen is        preferably chlorine, bromine or iodine, or a carbonyl group, an        anhydride group),    -   A₁ and A₂: are preferably a covalent bond, an alkyl group, an        alkenyl group, an alkynyl group, an alkoxy group, an alkylthio        group, a haloalkyl group, a haloalkoxy group, a cycloalkyl        group, a cycloalkoxy group, an aryl group, a heteroaryl group,        an aryloxy group, an aralkyl group, a monoalkylamino group, a        dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl        group, an alkynylcarbonyl group, a carboxylic ester group, a        carboxamide group, a sulphonic ester group, where a covalent        bond or an alkyl group as A₁ and A₂ is particularly        advantageous,    -   n: is an integer greater than or equal to 2.

The preparation of the compound of the inventive general formula I bypolymer-analogous reaction from the abovementioned compounds I″ and P′and the preparation thereof is shown in Schemes 8-13 below, but is notrestricted thereto.

R₂₉ is preferably a hydrogen atom, an alkyl group, an alkenyl group, analkynyl group, an alkoxy group, an alkylthio group, a cycloalkyl group,a cycloalkoxy group, an aryl group, a heteroaryl group, an aryloxygroup, an aralkyl group. More preferably, R₂₉ is an alkyl group.

Methods known per se are sufficient for synthesis of the compound of theabovementioned inventive general formula I according to Schemes 8-13.

If X″ in the general formula I″ corresponds to an isocyanate group, thecompound of the formula I can be synthesized by reaction of the compoundI″ with the compound P′ by a known method of urethane synthesis andderivatives thereof. Preferably, the abovementioned compound I issynthesized within a temperature range from −78 to 150° C.,advantageously within a temperature range from −40 to 120° C., in asolvent and in a reaction time of 0.1 to 100 hours. There are barely anyrestrictions for solvents used. Preference is given to aprotic organicsolvents, for example N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulphoxide, N-methylpyrrolidone, dichloromethane,1,2-dichloroethane, toluene, xylene, chlorobenzene or o-dichlorobenzene.

If X″ in the general formula I″ corresponds to a carboxylic acid group,the compound of the formula I can be synthesized by reaction of thecompound I″ with the compound P′ by a known method of carboxylic estersynthesis and derivatives thereof. Preferably, the abovementionedcompound I is synthesized within a temperature range from −78 to 150°C., advantageously within a temperature range from −40 to 12Q° C., in asolvent and in a reaction time of 0.1 to 100 hours, using a catalyst,for example a pyridine derivative such as typically4-(dimethylamino)pyridine, or a carbodiimide derivative such astypically N,N′-dicyclohexylcarbodiimide. There are barely anyrestrictions for solvents used. Preference is given to aprotic organicsolvents, for example N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulphoxide, N-methylpyrrolidone, dichloromethane,1,2-dichloroethane, toluene, xylene, chlorobenzene or o-dichlorobenzene.

If X″ in the general formula I″ corresponds to a carboxylic acid group,the compound of the formula I can be synthesized by reaction of thecompound I″ with the compound P′ by a known method of carboxylic estersynthesis and derivatives thereof. Preferably, the abovementionedcompound I is synthesized within a temperature range from −78 to 150°C., advantageously within a temperature range from −40 to 12Q° C., in asolvent and in a reaction time of 0.1 to 100 hours, using a catalyst,for example a pyridine derivative such as typically4-(dimethylamino)pyridine, or a carbodiimide derivative such astypically N,N′-dicyclohexylcarbodiimide. There are barely anyrestrictions for solvents used. Preference is given to aprotic organicsolvents, for example N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulphoxide, N-methylpyrrolidone, dichloromethane,1,2-dichloroethane, toluene, xylene, chlorobenzene or o-dichlorobenzene.

If X″ in the general formula I″ corresponds to a halogen atom, thecompound of the formula I can be synthesized by reaction of the compoundI″ with the compound P′ by a known method of ether synthesis andderivatives thereof. Preferably, the abovementioned compound I issynthesized within a temperature range from −78 to 150@C, advantageouslywithin a temperature range from −40 to 120° C., in a solvent and in areaction time of 0.1 to 100 hours, using a catalyst, for example a basesuch as sodium hydride, sodium hydroxide, potassium tert-butoxide, DBUor DBN. There are barely any restrictions for solvents used. Preferenceis given to a prone organic solvents, for example N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulphoxide, N-methylpyrrolidone,dichloromethane, 1,2-dichloroethane, toluene, xylene, chlorobenzene oro-dichlorobenzene.

If X″ in the general formula I″ corresponds to a carbonyl group, thecompound of the formula I can be synthesized by reaction of the compoundI″ with the compound P′ by a known method of acetal synthesis andderivatives thereof. Preferably, the abovementioned compound I issynthesized within a temperature range from −78 to 150° C.,advantageously within a temperature range from −40 to 120° C., in asolvent and in a reaction time of 0.1 to 100 hours, using a catalyst,for example protic acids such as p-toluenesulphonic acid, hydrochloricacid, sulphuric acid or trifluoroacetic acid. There are barely anyrestrictions for solvents used. Preference is given to aprotic organicsolvents, for example N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulphoxide, N-methylpyrrolidone, dichloromethane,1,2-dichloroethane, toluene, xylene, chlorobenzene or o-dichlorobenzene.

If X″ in the general formula I″ corresponds to an anhydride group, thecompound of the formula I can be synthesized by reaction of the compoundI″ with the compound P′ by a known method of carboxylic ester synthesisand derivatives thereof. Preferably, the abovementioned compound I issynthesized within a temperature range from −78 to 150° C.,advantageously within a temperature range from −40 to 120° C., in asolvent and in a reaction time of 0.1 to 100 hours, using a catalyst,for example a pyridine derivative such as typically4-(dimethylamino)pyridine, or a carbodiimide derivative such astypically N,N′-dicyclohexylcarbodiimide. There are barely anyrestrictions for solvents used. Preference is given to aprotic organicsolvents, for example N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulphoxide, N-methylpyrrolidone, dichloromethane,1,2-dichloroethane, toluene, xylene, chlorobenzene or o-dichlorobenzene.

In addition, the oligomeric or polymeric compounds of the inventivegeneral formula I are synthesized by polymer-analogous reaction of an11,11,12,12-tetracyanoanthraquinodimethane compound of the generalformula I′″ with an oligomeric or polymeric compound of the generalformula P″.

where

-   -   R₁ to R₇ and R₃₀ to R₃₂: may preferably each independently be        hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups,        alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy        groups, cycloalkyl groups, cycloalkoxy groups, aryl groups,        heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic        acid groups, sulphonic acid groups, amino groups, monoalkylamino        groups, dialkylamino groups, nitro groups, cyano groups,        alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl        groups, carboxylic ester groups, carboxamide groups, sulphonic        ester groups, halogen atoms or a combination of these groups or        atoms, particular preference being given to hydrogen atoms as at        least five of the R₁ to R₇ substituents and to non-hydrogen        atoms, preferably halogen atoms, alkyl groups, alkoxy groups,        cyano groups and/or nitro groups, as zero to two of the R₁ his        R₇ substituents, and/or to hydrogen atoms as at least two of the        R₃₀ to R₃₂ substituents and to non-hydrogen atoms, preferably        halogen atoms, alkyl groups, alkoxy groups, cyano groups and/or        nitro groups, as zero to one of the R₃₀ to R₃₂ substituents,    -   X′″: is a nucleophilic organic group which nucleophilically        attacks the atom adjacent to the halogen atom of the compound P″        and hence forms a covalent bond between the compound I′″ and P″,        preference being given to a hydroxyl group or a thiol group as    -   A₃ and A₄: are preferably a covalent bond, an alkyl group, an        alkenyl group, an alkynyl group, an alkoxy group, an alkylthio        group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a        heteroaryl group, an aryloxy group, an aralkyl group, a        dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl        group, an alkynylcarbonyl group, a carboxylic ester group, a        carboxamide group, a sulphonic ester group, particular        preference being given to a covalent bond or an alkyl group as        A₁ and A₂,    -   n: is an integer greater than or equal to 2.

The preparation of the compound of the general formula I with the aid ofa polymer-analogous reaction from the abovementioned compounds I′″ andP″ is shown in Schemes 14-15 below, but is not restricted thereto.

If X″ in the general formula I″ corresponds to a hydroxy] group or athiol group, the compound of the formula 1 can be synthesized byreaction of the compound I′″ with the compound P″ by a known method ofether synthesis and derivatives thereof. Preferably, the abovementionedcompound I is synthesized within a temperature range from −78 to 150°C., advantageously within a temperature range from −40 to 120° C., in asolvent and in a reaction time of 0.1 to 100 hours, using a catalyst,for example a base such as sodium hydride, sodium hydroxide, potassiumtert-butoxide, DBU or DBN. There are barely any restrictions forsolvents used. Preference is given to aprotic organic solvents, forexample N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulphoxide, N-methylpyrrolidone, dichloromethane, 1,2-dichloroethane,toluene, xylene, chlorobenzene or o-dichlorobenzene.

In addition, the oligomeric or polymeric compounds of the inventivegeneral formula I are synthesized by polymer-analogous reaction of an11,11,12,12-tetracyanoanthraquinodimethane compound of the generalformula I″″ with an oligomeric or polymeric compound of the generalformula P′″.

where

-   -   R₁ to R₇ and R₃₃ to R₃₅: may preferably each independently be        hydrogen atoms, alkyl groups, alkenyl groups, alkoxy groups,        alkylthio groups, haloalkyl groups, haloalkoxy groups,        cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl        groups, aryloxy groups, aralkyl groups, carboxylic acid groups,        sulphonic acid groups, amino groups, monoalkylamino groups,        dialkylamino groups, nitro groups, cyano groups, hydroxyl        groups, alkylcarbonyl groups, alkenylcarbonyl groups,        alkynylcarbonyl groups, carboxylic ester groups, carboxamide        groups, sulphonic ester groups, thiol groups, halogen atoms or a        combination of these groups or atoms, particular preference        being given to hydrogen atoms as at least five of the R₁ to R₇        substituents and to non-hydrogen atoms, preferably halogen        atoms, alkyl groups, alkoxy groups, cyano groups and/or nitro        groups, as zero to two of the R₁ bis R₇ substituents, and/or to        hydrogen atoms as at least two of the R₃₃ to R₃₅ substituents        and to non-hydrogen atoms, preferably halogen atoms, alkyl        groups, alkoxy groups, cyano groups and/or nitro groups, as zero        to one of the R₃₃ to R₃₅ substituents,    -   A₅ and A₆: are preferably a covalent bond, an alkyl group, an        alkenyl group, an alkoxy group, an alkylthio group, a haloalkyl        group, a haloalkoxy group, a cycloalkyl group, a cycloalkoxy        group, an aryl group, a heteroaryl group, an aryloxy group, an        aralkyl group, a monoalkylamino group, a dialkylamino group, an        alkylcarbonyl group, an alkenylcarbonyl group, an        alkynylcarbonyl group, a carboxylic ester group, a carboxamide        group, a sulphonic ester group, particular preference being        given to a covalent bond, an aryl group or an alkyl group as A₅        and A₆,    -   n: is an integer greater than or equal to 2.

The preparation of the compound of the general formula I with the aid ofa polymer-analogous reaction from the abovementioned compounds I″″ andP′″ is shown in Scheme 16 below, but is not restricted thereto.

The compound of the formula 1 can also be synthesized by reaction of thecompound F″ with the compound P″ by a known method of the azide/alkyneclick reaction and derivatives thereof. Preferably, the abovementionedcompound I is synthesized within a temperature range from −78 to 150°C., advantageously within a temperature range from −40 to 120° C., in asolvent and in a reaction time of 0.1 to 100 hours. There are barely anyrestrictions for solvents used. Preference is given to aprotic organicsolvents, for example N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulphoxide, N-methylpyrrolidone, dichloromethane,1,2-dichloroethane, toluene, xylene, chlorobenzene or o-dichlorobenzene.

The oligomeric or polymeric compounds of this invention canappropriately be used as redox-active material for storage of electricalenergy in an electrical charge storage means. A redox-active materialfor storage of electrical energy is a material which can store iselectrical charge and release it again, for example by accepting andreleasing electrons. This material can be used, for example, as anactive electrode material in an electrical charge storage means. Suchelectrical charge storage means for storage of electrical energy are,for example, secondary batteries (accumulators), redox flow batteriesand supercapacitors.

A secondary battery consists of a negative electrode and a positiveelectrode which are separated from one another by a separator, and anelectrolyte which surrounds the electrodes and the separator.

The separator is a porous layer which permits balancing of charge bybeing ion-permeable. The electrolyte is either a solvent with a saltdissolved therein or an oligomeric or polymeric ion-conducting compound.The main object of the electrolyte is ion conductivity, which is neededto balance the charge.

An electrode may consist of a thin layer on a substrate, composed of acomposite containing at least one conductivity additive, at least onebinder additive and a redox-active material for charge storage, whichmay be the oligomeric or polymeric compound of the inventive generalformula I. This composite is applied to a substrate with the aid of anelectrode slurry.

Said layer on the substrate is formed, for example, by using a knownmethod of film formation and derivatives thereof, preferably by variousprinting processes such as offset printing, screen printing, inkjetprinting, or else by a dip-coating method, or a spin-coating method, inwhich case the layer including the oligomeric or polymeric compound ofthe inventive general formula I is processed with the aid of anelectrode slurry. In this case, the oligomeric or polymeric compound ofthe invention, the conductivity additive and the binder additive may besuspended or dissolved in a solvent. The thickness of the abovementionedlayer containing the oligomeric or polymeric compound of this inventionis unlimited, but is preferably between 0.001 and 5000 μm, morepreferably between 0.01 and 1000 μm.

The substrates used for the abovementioned electrodes are layers ofconductive materials, preferably metals, such as platinum, gold, iron,copper, aluminium, lithium or a combination of these metals, and carbonmaterials, for example glassy carbon, graphite foil, graphene or carbonsheets, and oxide substances, for example indium tin oxide (ITO), indiumzinc oxide (IZO), antimony zinc oxide (AZO), fluorine tin oxide (FTO) orantimony tin oxide (ATO).

Conductivity additives used for the layer are independently one or moreelectrically conductive materials, preferably carbon materials, forexample carbon fibres, carbon nanotubes, graphite, carbon black orgraphene, and electrically conductive polymers, for examplepolyanilines, polythiophenes, polyacetylenes, PEDOT:PSS or polyacenes.Particular preference is given to using carbon fibres.

Binder additives used for the substrate may independently be one or morematerials having binder properties, preferably polymers, for examplepolytetrafluoroethylene, polyvinylidene fluoride,polyhexafluoropropylene, polyvinyl chloride, polycarbonate, polystyrene,polyacrylates, polymethacrylates, polysulphones, cellulose derivatives,and polyurethanes.

The electrode slurry is a solution or suspension consisting of anydesired proportions of a redox-active material for storage of electricalenergy, for example the oligomeric or polymeric compound of thisinvention as per formula I, a conductivity additive and a hinderadditive. Preferably, proportions of 5 to 100 percent by weight of aredox-active material for storage of electrical energy, 0 to 80 percentby weight of a conductivity additive and 0 to 10 percent by weight of abinder additive are used. Solvents used for the electrode slurry areindependently one or more solvents, preferably solvents having a highboiling point, for example N-methyl-2-pyrrolidone, water, dimethylsulphoxide, ethylene carbonate, propylene carbonate, dimethyl carbonate,methyl ethyl carbonate, gamma-butyrolactone, tetrahydrofuran, dioxolane,sulpholane, N,N-dimethylformamide or N,N-dimethylacetamide. Theconcentration of the redox-active material for storage of electricalenergy in the abovementioned electrode slurry is preferably between 0.1and 10 mg/ml, more preferably between 0.5 and 5 mg/ml.

The oligomeric or polymeric compounds of this invention as per generalformula I may, according to the counterelectrode used, be used as activematerial for electrical charge storage either for the negative electrodeor for the positive electrode.

If the oligomeric or polymeric compound of this invention as per formulaI is used as redox-active material for electrical charge storage in thepositive electrode, the redox-active material used for electrical chargestorage in the negative electrode is an active material which exhibits aredox reaction at a lower electrochemical potential than the oligomericor polymeric compound of this invention as per formula I. Preference isgiven here to using carbon materials, for example graphite, graphene,carbon black, carbon fibres or carbon nanotubes, and also metals oralloys, for example lithium, sodium, magnesium, lithium-aluminium,Li—Si, Li—Sn, Li—Ti, Si, SiO, SiO₂, Si—SiO₂ complex, Zn, Sn, SnO, SnO₂,PbO, PbO₂, GeO, GeO₂, O₂, MoO₂, Fe₂O₃, Nb₂O₅, TiO₂, Li₄Ti₅O₁₂, andLi₂Ti₃O₇.

If the oligomeric or polymeric compound of this invention as per formulaI is used as redox-active material for electrical charge storage in thenegative electrode, the redox-active material used for electrical chargestorage in the positive electrode is an active material which exhibits aredox reaction at a higher electrochemical potential than the oligomericor polymeric compound of this invention as per formula 1. Preference isgiven here to using organic redox-active material for electrical chargestorage, for example an oligomeric or polymeric compound having a stableorganic radical, an oligomeric or polymeric compound having anorganosulphur unit, an oligomeric or polymeric compound having a quinonestructure, an oligomeric or polymeric compound having a dione system, anoligomeric or polymeric compound having a disulphide bond and anoligomeric or polymeric compound having a phenanthrene structure andderivatives thereof or redox-active inorganic material for chargestorage, for example LiCO₂, LiMn₂O₄, LiNiO₂, LiNi_(0.5)Mn_(0.5)O₂,LiFePO₄, LiMnO₄, LiCoPO₄, or LiMnSiO₄. If an abovementioned redox-activeoligomeric or polymeric compound is used in the positive electrode, thiscompound may also be a composite consisting of this oligomeric orpolymeric compound, a conductivity additive and a binder additive in anyratio. This composite may, as described above, be present as a layer ona substrate through a known film-forming process with the aid of anelectrode slurry.

The redox-active material used for charge storage may also beair/oxygen. In this case, the positive electrode may consist of aconductivity additive, a binder additive and a redox catalyst.Preferably, redox catalysts used are an inorganic redox-active material,for example manganese oxide, or a redox-active organic material, forexample an organic radical.

The abovementioned separator used in said secondary battery is a porousmaterial, preferably membrane consisting of a polymeric compound, forexample polyolefin, polyamide or polyester. The task of the separator isto separate the positive electrode from the negative electrode and toenable balancing of charge through permutation of ions.

The abovementioned electrolyte of said battery may be either a liquid oran oligomeric or polymeric compound having high ion conductivity.

If the electrolyte is liquid, it is independently composed of one ormore solvents and one or more conductive salts.

The solvent of the electrolytes preferably consists independently of oneor more solvents having a high boiling point and high ion conductivitybut low viscosity, for example acetonitrile, dimethyl sulphoxide,ethylene carbonate, propylene carbonate, dimethyl carbonate, diethylcarbonate, methyl ethyl carbonate, gamma-butyrolactone, tetrahydrofuran,dioxolane, 1,2-dimethoxymethane, 1,2-dimethoxyethane, diglyme, triglyme,tetraglyme, ethyl acetate, 1,3-dioxolane or water.

The conductive salt in the electrolyte consists of a cation of theformula M^(e+) and an anion of the formula An^(f−) of the formula(M^(e+))_(a)(An^(f−))_(b) where e and f are integers depending on thecharge of M and An; a and b are integers which represent the molecularcomposition of the conductive salt.

Cations used in the abovementioned conductive salt are positivelycharged ions, preferably metals of the first and second main groups, forexample lithium, sodium, potassium or magnesium, but also other metalsof the transition groups, such as zinc, and organic cations, for examplequaternary ammonium compounds such as tetraalkylammonium compounds.

Anions used in said conductive salt are preferably inorganic anions suchas hexafluorophosphate, tetrafluoroborate, triflate, hexafluoroarsenate,hexafluoroantimonate, tetrafluoroaluminate, tetrafluoroindate,perchlorate, bis(oxalato)borate, tetrachloroaluminate,tetrachlorogallate, but also organic anions, for example N(CF₃SO₂)₂ ⁻,CF₃SO₃ ⁻, alkoxides, for example tert-butoxide or i-propoxide, but alsohalides such as fluoride, chloride, bromide and iodide.

EXAMPLES

The invention is to be illustrated in detail hereinafter by the working,examples for preparation and use shown in the drawings.

The drawings show:

FIG. 1: Cyclic voltammograms of a monomer prepared according to Example2 (broken line) and of an electrode produced therefrom according toExample 4 (solid line)

FIG. 2: Charge/discharge curves of the first (solid line) and fivehundredth (broken line) charging/discharging cycle of a secondarybattery produced according to Example 5

FIG. 3: Charging/discharging behaviour of the secondary battery producedaccording to Example 5

FIG. 4: Coulomb efficiency of the secondary battery produced accordingto Example 5

¹H and ¹³C NMR spectra were recorded with a Broker AC 300 (300 MHz)spectrometer at 298 K. Elemental analyses were conducted with a VarioELIII-Elementar Euro instrument and an EA-HekaTech instrument. Forcyclic voltammetry and galvanostatic experiments, a Biologic VMP 3potentiostat was available. Size exclusion chromatography was conductedon an Agilent 1200 series system (degasser: PSS, pump: G1310A,autosampler: G1329A, oven: Techlab, DAD detector: G1315D, RI detector:G1362A, eluent: DMAc+0.21% LiCl, 1 ml/min, temperature: 40° C., column:PSS GRAM guard/1000/30 Å).

Example 1 Synthesis of 2-vinylanthraquinone (3)

2-Bromoanthraquinone (1.5 g, 5.22 mmol),bis(dibenzylideneacetone)palladium(0) (0.060 g, 0.104 mmol),biphenyl-2-yldi-tert-butylphosphine (0.062 g, 0.209 mmol) are dissolvedin a 0.3 M solution of tetrabutylammonium fluoride in tetrahydrofuran.The solution is purged with argon, and2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-1,3,5,7,2,4,6,8-tetraoxatetrasiloxane(0.902 nil, 2.61 mmol) is added dropwise. The mixture is stirred at 80°C. under an argon atmosphere for 8 hours. The reaction mixture is cooledto room temperature and added to 250 ml of ethanol. The precipitate isfiltered off and washed twice with n-hexane. After drying under reducedpressure, almost pure 2-vinylanthraquinone (3) (1.175 g, 5.02 mmol, 96%)is obtained as a yellowish solid, the purity of which is sufficient forthe next reaction step.

Anal. Calcd for C₁₆H₁₀O₂: C, 81.90; H, 4.30. Found: C, 81.85; H, 4.31.¹H NMR (CDCl₃, 300 MHz, ppm): δ 5.54 (d, 1H), 6.05 (d, 1H), 6.87 (dd,1H), 7.80 (m, 3H), 8.32 (m, 4H). ¹³C NMR (CDCl₃, 75 MHz, ppm): δ 183.2,182.6, 143.2, 135.4, 134.1, 134.0, 133.8, 133.6, 133.5, 132.5, 131.4,128.3, 127.8, 127.2, 124.8, 118.4.

Example 2 Synthesis of2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane (4)

2-Vinylanthraquinone (1 g, 4.27 mmol) and malononitrile (0.85 g, 0.81ml, 12.81 mmol) are dissolved in 71 ml of chloroform. Pyridine (2.07 ml,25.6 mmol) and titanium tetrachloride (1.41 ml, 12.81 mmol) are addeddropwise to the reaction mixture within five minutes. The mixture isstirred at 80° C. under argon for 15 hours, cooled to room temperatureand extracted twice with water and once with brine. The organic phase isdried with sodium sulphate, the desiccant is filtered off and theorganic phase is concentrated under reduced pressure. The crude productis purified by column chromatography (silica gel, chloroform). Thisgives 700 mg of 2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane (4)(2.12 mmol, 50%) as a yellow powder.

Anal. Calcd for C₂₂H₁₀N₄: C, 80.00; H, 3.10, N, 16.90. Found: C, 79.94;H, 3.08. N, 16.91. ¹H NMR (CD₂Cl₂, 300 MHz, ppm): δ 5.61 (d, 1H), 6.06(d, 1H), 6.88 (dd, 1H), 7.77 (m, 3H), 8.27 (m, 4H). ¹³C NMR (CD₂Cl₂, 75MHz, ppm): δ 160.5, 160.0, 141.8, 134.5, 132.4, 130.8, 130.4, 130.2,129.7, 129.0, 128.01, 127.5, 124.93, 119.3, 113.3, 113.1.

Example 3 Synthesis ofpoly(2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane) (5)

50 mg of 2-vinyl-11,11,12,12-tetracyanoanthraqumodimethane (4) aredissolved in 0.150 ml of N,N-dimethylformamide, and 1.24 mg of AIBN(0.0076 mmol, 5 mol %) are added. The reaction mixture is degassed withargon for five minutes and stirred at 80° C. for 18 hours. Thereafter,the reaction solution is added to 50 ml of dichloromethane, in order toprecipitate the product. This forms 42 mg ofpoly(2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane) (5) as a yellowsolid.

Anal. Calcd for C₂₂H₁₀N₄: C, 80.00; H, 3.10, N, 16.90. Found: C, 79.96;H, 3.13, N, 16.95. ¹H NMR (DMF-d₇, 300 MHz, ppm): δ 8.83 to 7.48 (br,7H), 2.62 to 1.31 (br, 3H). SEC: M_(n) 2.67×10⁴ g/mol 1.87.

Example 4 Production of an electrode withpoly(2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane) (5), cf. FIG. 1

A solution consisting ofpoly(2-vinyl-11,11,12,12-tetracyanoanthraquinodimethane) (5) in NMP(N1-methyl-2-pyrrolidone) (10 mg/ml) was added to carbon fibres (VGCF;Showa-Denko) and Super P® as conductivity additives and poly(vinylidenefluoride) (PVDF; Sigma Aldrich) as binder additives (ratio: 20/30/30/10wt %). These materials were mixed in a mortar for 10 minutes, and theresulting paste was applied to an aluminium foil using a coating blademethod (thickness: 0.015 mm, MTI Corporation). The electrode is dried at100° C. for 24 hours.

The electrode is dipped into an electrolyte solution (0.1 M LiClO₄ inpropylene carbonate). For the cyclic voltammetry measurement, ahalf-cell consisting of said electrode as working electrode and anAg/AgNO₃ electrode as reference electrode, and also a platinum mesh ascounterelectrode, is constructed, (FIG. 1)

The cyclic voltammogram shows a stable redox reaction at −0.71 V.

Example 5

Production of an Li Polymer Battery

The electrode described in Example 4 is introduced into a secondarybattery (Li polymer battery) under an argon atmosphere. The electrolyteused is a 0.1 M solution of LiClO₄ in propylene carbonate; thecounterelectrode used is a piece of elemental lithium. The twoelectrodes are separated from one another by the separator (a porouspolypropylene membrane, Celgard). The battery shows a charge plateau at2.9 V and a discharge plateau at 2.4 V (FIG. 2).

In the first charge/discharge cycle, the battery shows a capacity of 156mAh/g (97% of the theoretically possible capacity); after 500charge/discharge cycles, the battery shows a capacity of 141 mAh/g (FIG.3) at an average coulomb efficiency of 99%. (FIG. 4)

The invention claimed is:
 1. A tetracyanoanthraquinodimethane polymercomprising an oligomeric or polymeric compound of formula I:

where R₁ to R₇: are each independently hydrogen atoms, alkyl groups,alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups,haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxygroups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups,carboxylic acid groups, sulphonic acid groups, amino groups,monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups,hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups,alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups,sulphonic ester groups, thiol groups, halogen atoms or a combination ofthese groups or atoms, X: an organic group of one of the generalformulae II-XIV:

wherein R₈ to R₂₄: are each independently hydrogen atoms, alkyl groups,alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups,haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxygroups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups,carboxylic acid groups, sulphonic acid groups, amino groups,monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups,hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups,alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups,sulphonic ester groups, thiol groups, halogen atoms or a combination ofthese groups or atoms, R₃₀ to R₃₂: are each independently hydrogenatoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups,alkylthio groups, haloalkyl groups, haloalkoxy groups cycloalkyl groups,cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups,aralkyl groups, carboxylic acid groups, sulphonic acid groups, aminogroups, monoalkylamino groups, dialkylamino groups, nitro groups, cyanogroups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups,alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups,sulphonic ester groups, thiol groups, halogen atoms or a combination ofthese groups or atoms, R₃₀ to R₃₂: are each independently hydrogenatoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups,alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkylgroups, cycloalkoxy groups, aryl groups, heteroacyl groups, aryloxygroups, aralkyl groups, carboxylic acid groups, sulphonic acid groups,amino groups, monoalkylamino groups, dialkylamino groups, nitro groups,cyano groups, alkylcarbonyl groups, alkenylcarbonyl group,alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups,sulphonic ester groups, halogen atoms or a combination of these groupsor atoms, R₃₃ to R₃₅: are each independently hydrogen atoms, alkylgroups, alkenyl groups, alkoxy groups, alkylthio groups, haloalkylgroups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy group, arylgroups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylicacid groups, sulphonic acid groups, amino groups monoalkylamino groups,dialkylamino groups, nitro groups, cyano groups, hydroxyl groups,alkylcarbonyl groups, alkenylcarbonyl groups, alkylcarbonyl groups,carboxylic ester groups, carboxamide groups, sulphonic ester groups,thiol groups, halogen atoms or a combination of these groups or atoms,A: is an oxygen atom, a sulphur atom or an —N(R₂₉)— group, where R₂₉ isa hydrogen atom, alkyl group, alkenyl group, alkynyl group, alkoxygroup, alkylthio group, haloalkyl group, haloalkoxy group, cycloalkylgroup, cycloalkoxy group, aryl group, heteroacyl group, aryloxy group,aralkyl group, carboxylic acid group, sulphonic acid group, nitro group,alkylcarbonyl group, alkenylcarbonyl group, alkynylcarbonyl group,carboxylic ester group, carboxamide group, or sulphonic ester group, A₁and A₂: are each independently a covalent bond, an alkyl group, analkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, ahaloalkyl group, a haloalkoxy group, a cycloalkyl group, a cycloalkoxygroup, an aryl group, a heteroaryl group, an aryloxy group, an aralkylgroup, a monoalkylamino group, a dialkylamino group, an alkylcarbonylgroup, an alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylicester group, a carboxamide group, or a sulphonic ester group, A₃ and A₄:are each independently a covalent bond, an alkyl group, an alkenylgroup, an alkynyl group, an alkoxy group, an alkylthio group, acycloalkyl group, a cycloalkoxy group, an aryl group, a heteroarylgroup, an aryloxy group, an aralkyl group, a dialkylamino group, analkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group,a carboxylic ester group, a carboxamide group, or a sulphonic estergroup, A₅ and A₆: are each independently a covalent bond, an alkylgroup, an alkenyl group, an alkoxy group, an alkylthio group, ahaloalkyl group, a haloalkoxy group, a cycloalkyl group, a cycloalkoxygroup, an aryl group, a heteroaryl group, an aryloxy group, an aralkylgroup, a monoalkylamino group, a dialkylamino group, an alkylcarbonylgroup, an alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylicester group, a carboxamide group, a sulphonic ester group, Ar: is anindependently substituted cycloalkyl group, cycloalkoxy group, arylgroup, heteroaryl group, aryloxy group, or aralkyl group, and n: is aninteger greater than or equal to
 2. 2. Thetetracyanoanthraquinodimethane polymer according to claim 1, wherein atleast five of R₁ to R₇ are hydrogen and zero to two of R₁ to R₇ arehalogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groupsand/or other non-hydrogen substitutents.
 3. Thetetracyanoanthraquinodimethane polymer according to claim 1, wherein atleast two of the R₈ to R₁₀ substituents are hydrogen atoms and zero totwo of the R₈ to R₁₀ substituents are halogen atoms, alkyl groups,alkoxy groups, cyano groups, nitro groups and/or other non-hydrogen atomsubstituents, and/or wherein at least two of the R₁₁ to R₁₃ substituentsare hydrogen atoms and zero to two of the R₁₁ to R₁₃ substituents arehalogen atoms, alkyl groups, alkoxy groups, cyano groups, nitro groupsand/or other non-hydrogen atom substituents, and/or wherein R₁₄ is ahydrogen atom, and/or wherein at least two of the R₁₅ to R₁₇substituents are hydrogen atoms and zero to two of the R₈ to R₁₀substituents are halogen atoms, alkyl groups, alkoxy groups, cyanogroups, nitro groups and/or other non-hydrogen atom substituents, and/orwherein at least two of the R₁₈ to R₂₀ substituents are hydrogen atomsand zero to two of the R₁₈ to R₂₀ substituents are halogen atoms, alkylgroups, alkoxy groups, cyano groups, nitro groups and/or othernon-hydrogen atom substituents, and/or wherein R₂₁ is a hydrogen atom,and/or wherein at least two of the R₂₂ to R₂₄ substituents are hydrogenatoms and zero to two of the R₂₂ to R₂₄ substituents are halogen atoms,alkyl groups, alkoxy groups, cyano groups, nitro groups and/or othernon-hydrogen atom substituents, and/or wherein at least two of the R₂₆to R₂₈ substituents are hydrogen atoms and zero to two of the R₂₆ to R₂₈substituents are halogen atoms, alkyl groups, alkoxy groups, cyanogroups, nitro groups and/or other non-hydrogen atom substituents, and/orwherein at least two of the R₃₀ to R₃₂ substituents are hydrogen atomsand zero to two of the R₃₀ to R₃₂ substituents are halogen atoms, alkylgroups, alkoxy groups, cyano groups, nitro groups and/or othernon-hydrogen atom substituents, and/or wherein at least two of the R₃₃to R₃₅ substituents are hydrogen atoms and zero to two of the R₃₃ to R₃₅substituents are halogen atoms, alkyl groups, alkoxy groups, cyanogroups, nitro groups and/or other non-hydrogen atom substituents.
 4. Thetetracyanoanthraquinodimethane polymer according to claim 1, wherein Ais an oxygen atom.
 5. The tetracyanoanthraquinodimethane polymeraccording to claim 1, wherein A₁ and A₂ and A₃ and A₄, are a covalentbond or an alkyl group and A₅ and A₆ are a covalent bond, aryl group oran alkyl group.
 6. An active electrode material for a secondary batteryor other electrical charge storage device comprising thetetracyanoanthraquinodimethane polymer according to claim
 1. 7. A fullor partial surface coating of electrode elements for a secondary batteryor other electrical charge storage device comprising thetetracyanoanthraquinodimethane polymer according to claim
 1. 8. Anelectrode slurry for a secondary battery or an electrical charge storagedevice, comprising the tetracyanoanthraquinodimethane polymer accordingto claim 1.